Single pad-steam process for dyeing cellulosic materials



. haust and printing procedures.

United States Patent This application is a continuation-in-part application of gcipergding application Serial No. 154,028, filed November 1 61. This invention relates to compositions of matter useful as reactive dyes for materials possessing in their structure exchangeable hydrogen atoms. More particularly, this invention deals with dyes for textile fibers and similar organic materials (including paper, leather, plastic film, etc.) which possess in their molecules or micelles reactive radicals such as OH, NH or NH Common illustrations of such materials are cellulosic fiber, wool, silk, nylon fiber and polyvinyl alcohol It is an object of this invention to provide novel chemical compounds adapted for use as fiber-reactive dyes. Another object is to provide fiber-reactive dyes which are versatile in the sense that they can be applied to the,

fiber by various standard methods such as padding, ex= A further object is to provide fiber-reactive dyes which can 'be manufactured economically and which generally give rapid and high fixation on cellulosic fibers. Still another object is to provide fiber-reactive dyes which possess good build-up qualities and which produce dyeings that are fast to light and to washing. Other objects and achievements of this invention will appear as the description proceeds.

By rapid fixation in this application, we mean essentially complete fixation after 0.5 to one minute. (This quality is ofinterest primarily in padding procedures.) By high fixation, we mean that about 70 to 100% of the dye is chemically bonded to the fiber. j

Reactive dyes constitute .a type of dyes of relatively recent development. 'In these dyes, the dyeing capacity depends, not on physical afiinity between the dye and fiber, but on direct chemical reaction (with formation of covalent bonds) between the dye and certain reactive radicals in the fiber. Such dyes generally have the form Sol. i

wherein D is the essential radical of a dye molecule, in other words, a radical containing a chromophoric group; S01. is a solubilizing group, such as sulfo or carboxy; and Q is a reactive radical through which the dye molecule is reacted with the OH groups or NH or NH groups of the fiber.

Heretofore, monochloroand dichlorotriazine radicals have generally been used as reactive radicals, although others have been suggested or actually used.

Now, according to the present invention, new chemical compounds are produced which may be used as reactive dyes on fiber or other organic material as aforementioned, and satisfying to a high degree the aforenoted objects and improvements. The new chemical compounds may be expressed by the general formula D-NCO-Q I l wherein D is the radical of a water-soluble dye chromophore, particularly of an azo, metallized azo, acid-anthra- 3,256,054 Patented June 14, 1966 acid or water-soluble salt); and Q is the radical of a benzodiazine of the group consisting of quinoxalines and p'hthalazines bearing two halogen atoms in the heterocyclic ring and being attached to the CO group in the above formula in the benzo ring.

More particularly, Q is a dihalogenobenzodiazine radical of the group defined by the formulas and wherein each X individually designates C1 or Br.

The novel dye compounds of this invention are readily and economically prepared by reacting a water-soluble amino-dye compound of the formula 'D-NHR, wherein D and R have the same meaning as above, with a B2- carbonyl halide of a benzodiazine compound as above defined, in other words, a compound of the formula QCOhal., wherein hal represents a halogen atom such as C1 or Br While Q is a benzodiazine compound selected from the group above set forth. The reaction is achieved by bringing the two reactants together in aqueous solution at room temperature (or higher, if desired (up to say C.)', in the presence of an alkali-metal carbonate or other convenient acid-binding agent (NaOH, Na PO pyridine, etc.) in sufiicient quantity to drive the condensation forward at a reasonable rate. customarily, a pH between 6 and 10 will answer this purpose. The reaction product is recovered by salti'ng out and filtering, in the usual manner.

The requisi-te'diha-logeno benzodiazine carbonyl halide itself may be prepared by the action of a phosphorus pentahalide or oxyhalide on the corresponding dihydroxybenzodiazine canboxylic acid. Dihalogeno benzodi-azine carbonyl halides wherein the two X-atoms are unlike may be obtained in the same manner except using a mixture of phosphorus pentachlbride and phosphorus pentabro- 'mide, for instance, or of phosphorus oxychloride and phosphorus oxybromide In the cases where D is an .azo dye, other methods of synthesis are also available; for instance, 1) condensing the benzodtiazline carbonyl halide with an azo-dye coupling component, and then coupling the condensed product to a di-azotized arylanrine or azoarylamine compound, (2) condensing the benzodiazine carbonyl halide, in equimolecular proportions, with an aryl diarnline; diazo'tizing cedures such as padding, exhaust, printing or (in the case of azo dyes) development on the lfiber. All these procedures involve at one stage or another treatment of the fabric also with an aqueous alk-ali'solution and heating. For instance, in padding, two separate baths may be employed, whereby the fabric is first padded in a dyebath then dried and padded in an alkaline bath; or the is generally incorporated in the printing paste, and the printed fabric is dried and heated. In exhaust technique, the alkaline agent is generally entered into the dyebath after exhaustion of the dye on the fiber has been achieved, for instance, by adding salt (NaCl) to the dyebath.

Where the dye is developed on the fiber, the alkaline and heating treatments are applied to the fiber after impregnation with :the component which carries the dih-alobenzodiazine-carbonyl radical, but before application of the 'further treatments necessary to develop an azo dye on the fiber.

The alkaline agents usable for the above purposes are of the same general class as normally used in dyeing with fiber-reactive dyes. Sodium carbonate and sodium hydroxide are the agents most commonly used, and the degree of alkalinity required its typified by a 2% aqueous solution thereof.

In forming the dyebath for padding or exhaustion, urea or other agents which assist in dissolving the color may .be added. In some cases, a concentrated aqueous solution of the dye may be prepared first, which is then diluted to a bath of the desired strength, or, in the case of printing, .is incorporated in the printing paste.

In all the above procedures, the novel dyes of the invention are Ifound to give both rapid and high fixation, and :the dyeings obtained are characterized by good fastness to light and to washing.

In the dyeing procedures, a reaction between dye and fiber is believed to take place as illustrated by the following typical equation.

In this equation, Cell represents a cellulose radical, G represents -a 5- or 6-benzodiazine radical of the group consisting of quinoxaline and phthalazine (which bears the Cl-atoms in the heterocyolic ring), while Y represents Cl, OH (resulting firom hydrolysis) or another O-Cell radical.

The above modes of application and theory of reaction apply also to other fibers which have OH, NH or NH;; radicals, but obviously high alkalinity or prolonged contact with alkali are to :be avoided in the case of wool or other fibers which are sensitive to alkali.

On the other hand, the novel dyes of this invention are applicable to wool and nylon also by the ordinary dyeing procedures recognized for these fibers, that is from -a hot, dilute acidic :bath as is customary in the art of dyeing with acid dyes.

Without limiting this invention, the following examples ar given to illustrate our preferred mode of operation. Parts mentioned are by weight.

PART I.PREPARATION OF DIHALO-BEN- ZODIAZINE CARBONYL HALIDES Example 1 .2,3-dicl1lor0-6-quinoxaline-carbonyl chloride 15 parts of 3,4-diaminobenzoic acid are added to 30 parts of 2B alcohol (95% ethanol) containing 9 parts of oxalic acid and 0.01 part of sulfuric acid. The resulting slurry is heated to reflux, held at reflux 12 to 15 hours, cooled and filtered. The filter cake, 2,3- dihydroxy-S-quinoxa-line carboxylic acid, is washed with O-Gell 10 parts of 2B alcohol, dried, and added to a mixture of 40 parts of phosphorus pentachloride and 30 parts of phosphorus oxychloride. The slurry is now heated to reflux, held at reflux for 3 to 4 hours, cooled, and poured into 200 to 300 parts of water which is maintained 25 to 35 C. by the addition of ice. The solid is filtered off, dried below 40 C., and recrystallized from 50 parts of cyclohexane, to yield 2,3-dichloro-6-quinoxaline-carbonyl chloride, of M.P. 112-113 C.

If the same procedure is carried out, except using 2,3- d-iaminobenzoic acid in lieu of the 3,4-diaminobenzoic acid above mentioned, 2,3-dichloro-5-quinoxaline-carbonyl chloride is obtained.

Example 2.1,4-dichlor0-6-phthalazine-carbonyl chloride To 24.6 parts of trimellitic anhydride slurried in parts of glacial acetic acid, is added at reflux temperature and over a one half hour period of solution of 5 parts of hydrazine hydrate in 30 parts of glacial acetic acid. The resulting slurry is refluxed 4 to 8 hours, cooled and filtered. The filter cake, 1,4-dihydroxy-6-phthalazine-carboxy-lic acid, is washed with 10 parts of glacial acetic acid, dried, and added to a mixture of 60 parts of phosphorus pentachloride and 15 parts of phosphorus oxychloride. The slurry is heated to reflux to C.), held for 3 to 4 hours at this temperature, cooled, and diluted with 70 parts of petroleum ether (B.P. 30 to 60 C.). The precipitated colorless solid is filtered, rinsed with 5 parts of ice-cold acetone, and

dried to yield 1,4-dichloro-6-phthalazine-carbonyl chloride, of M.P. l30132 C. In like manner, if hemimellitic anhydride is used in lieu of the trimellitic anhydride in the above example, l,4-dichloro-5-phthalazine-carbonyl chloride is obtained.

Example 3 By following the procedure of Example 1 or 2, except using a mixture of PBr and POBr in lieu of the mixture of PCl and POCl there indicated, the compounds 2,3-dibromo-6-quinoxaline carbonyl bromide and 1,4-dibrorno-6-phthalazine carbonyl bromide, respectively, are obtained.

PART II.PREPARATION OF FIBER-REACTIVE DYES Throughout these examples and tables which accompany them, an arrow inserted between the names of two compounds stands for the Words: diazotized and coupled 10.

Example I.Azo dye 8.9 parts of the azo dye, 2-amino-4,8-naphthalenedisulfonic acid-e3-aminoacetanilide, are dissolved in 250 parts of water. After adjusting the pH (by the aid of sodium bicarbonate) to about 8 and the temperature to 35 C., 5.0 parts of 2,3 dichloro 6 quinoxaline carbonyl chloride (prepared as in Example 1, above) are added. The mixture is stirred overnight at the above temperature and pH, then salted with 12 parts of sodium chloride, whereupon the precipitate formed is filtered off, washed with an aqueous (5%) NaCl solution and dried in a vacuum at a temperature below 60 C.

The light-yellow product obtained corresponds to the formula SOINB NaOJS ILHCOCH;

When this dye is applied to cotton fabric by the procednre of Examples A to C below, a bright yellow dyeing is obtained that exhibits excellent fastness to light, washing and acid perspiration, and has good bleach fastness.

A dye of similar shade anddyeing qualities is obtained if the quinoxaline compound above named is replaced by an equal weight of 1,4-dichloro-6-phthalazinecarbonyl chloride, prepared as in Example 2, above.

Dyes of similar high fastness qualities and of shades lI l'N H033 SOIH as indicated below are obtained by condensing the one or the other of the above named diazine carbonyl chloride compounds, according to the procedure of the above example, with any one of the following aminoazo dyes:

TABLE I Item Aminoazo dye Shade on No. Cotton 1 S-amino-l,3,6naphthalene-trisulionic acid-aniline Yellow. 2 8-amin0-1,3,6-naphthalene-trisulionic acid-+3- D0.

aminoacetanilide. V 3 Orthgnilic acld 6-amlno-1-naphthol-3-sulfonic. Orange.

ac] 4 2-arnino-p-benzenedisulionic acid. diazotized and coupled to:

(a) G-amino-1naphthol-3-sulfonic acid Do.- (b) 8-amino-1-naphthol-3,6-disulfonic acid Red. 5 2-amin0-4-methoxybenzene-sulfonic acid- 6- Orange amtno-l-naphthol-l-sulfonic acid. 6 1-(4-aminophenylazo)-2-naphthylarmne-2,3,6- Do. trisulionic acid. 7 Orthanilic acld 8-ami:no1-naphthol-3,6-d1sulion1c Red.

acid. 8 ,2-amino-4methylbenzene-sulionlc acid- 8-amiuo- Red. 1-naphtl1ol-3,6-disulionic acid. 9.-.--. 3-amino-5-methylbenzene-sulionic acid- 8-ammo- Red.

1-uaphthol-3,6disulionic acid. 10 3-an1ino-2,7-naphthalene-disultouie acid 8-amino- Red.

Luaphthol-Mrdisulfonic acid. 1l 1- -arninophenylazo)-2-naphthylamine-2,3,6-

trisulionic acid. diazotized and coupled to:

( Aniline Violet. (b) m-tnlnidina D0,

(The amino-monoazo compound named in items 6 and 11 above is obtained by reduction of the corresponding 4-nitrophenylazo compound, as described more fully in copending application of W. H. Gumprecht and D. J. Reif, Serial No. 830,733, filed July 31, 1959.).

The procedural details of the above example may likewise be varied considerably. For instance the volume of water used is not critical. In lieu of sodium bicarbonate, sodium hydroxide, trisodium phosphate and the like may be used to control the pH, and the latter may be kept at a value between 6 and 10. The condensation temperature may vary from 5 to 85 C., and the reaction time from 1 to 50 hours. The quantity of electrolyte used to salt out the product is likewise not critical.

Example II.Az0 dye 30 parts of the amino-azo dye 6 saturated aqueous sodium chloride, filtered off, washed with 4 parts of sodium chloride in parts of water, and dried below 70 C. in vacuum desiccator. The product is a sodium salt which in its free acid form corresponds to the formula dissolves in water to give a yellow solution.

When applied to cotton fabric by any of the procedures A to C hereinbelow, a bright yellow dyeing is obtained, which exhibits excellent fastness to light, washing, bleach, and acid perspiration.

The initial azo dye used in this procedure is itself a novel compound and comes withinthe scope of the claims of copending application of R. E. Starn, Jr., and W. H. Gumprecht, Serial No. 800,931, filed March 23, 1959. It may be prepared by procedure analogous to that set forth in Example 1 of said application, and which is, in brief outline, as follows:

4-amino-4'-nitrostilbene-2,2'-disulfonic acid is diazotized and coupled to 2-naphthylamine-3,6-disulfonic acid, and the resulting'solution is oxidized with alkaline sodium hypochlorite to form the naphtho-triazole compound. After recovery of the latter by salting out and filtration, it is redissolved in water at pH 4 (using acetic acid) and reduced with iron filings at C. After filtering, the solution of the resulting 4'-amino compound is diazotized, coupled in acid medium to N-rnethyl-aniline, and salted.

A dye of similar shade and good dyeing qualities is obtained if the procedure of this example is repeated except using as diazine reagent 2,3-dichloro-6-quinoxalinecarbonylchloride.

Dyes of similar high fastness qualities and of shades as indicated below arealso obtained by the same procedures as in this example, except for replacing the aminoazo dye there named by the stoichiometrically equivalent quantity of any of the aminoazo dyes listed in the following Table II:

TABLE II Shade on Cotton Aminoazo dye (a) N-n-butylaniline (b) N-methyl-m-toluidine Yellow.

Orange.

are dissolved at 40 C. in 600 parts of water. The red solution is cooled to 16 C., the pH is adjusted with sodium bicarbonate'to about 7.5 to 8.0, and 10 parts of 1,4- dich1oro-6-phthalazine-carbonyl chloride dissolved in parts of acetone are added; The resulting slurry is maintained at 10 to 20 for 3 hours, while the pH is maintained between 7 and 8 by the addition of an aqueous solution of sodium bicarbonate. The resulting yellow dye Example IlI.- Az0 dye-Alternate process-Condensing the carbonyl halide with the coupling component 15 parts of sodium formate. 26.2 parts of 2,3-dich1oro-6-- quinoxaline-carbonyl chloride are then added at 20 to is salted from solution by the addition of 200 parts of '75 25 C. and pH 4.5 to 5.2 (held constant by the addition of 2 N sodium carbonate) over a period of 4 hours. The condensation mass is stirred overnight at 20 to 25 C. and pH 4.5 to 5.0, then warmed to 50 C., and filtered. The filtrate is salted with 300 parts of sodium chloride, cooled to 18 C. and filtered. The resulting green-brown filter cake is slurried at'room temperature in 2000 parts of water, the pH is adjusted to 7.0 by addition of sodium bicarbonate, and 60 parts of sodium bicarbonate are added.

(b) Preparation of the diazo'solution and coupling. 25.3 parts of 2-amino-p-benzenedisulfonic acid in 600 parts of water are diazotized with sodium nitrite in the presence of HCl in the usual manner. The pH of the diazo solution is adjusted to 4.9 by addition of 2 N sodium carbonate, and the mass is then stirred into the above solution of coupling component, over a period of one hour. The resulting red solution is salted by adding 450 parts of sodium chloride. The red precipitate is filtered oif, washed with 50 parts of a 15% sodium chloride solution, and dried.

The color obtained is a sodium salt of the compound defined by the formula:

and when applied to cotton by the procedures of Examples A and C below, gives bright red dyeings which possess excellent fastness to light and washing, and good acid perspiration fastness.

(c) If 17.3 parts of orthanilic acid are used in place of the 25.3 parts of 2-amino-p-benzenedisulfonic acid in part (b) above, a sodium salt of the compound defined by the formula som on NHG o C431 HO S is obtained. This compound is of red-orange shade, and when applied to cotton by the procedures of Examples A to C below, it gives bright red dyeings of excellent fastness to light, washing and acid perspiration.

A dye of similar properties is obtained when S-a-mino-lnaphthol-3,6-disulfonic acid is condensed as above with 1,4-dic-h-loro-6-phthalazine-carbonyl chloride, and then coupled to diazotized orthanilic acid.

Other fiber-reactive dyes of high fastness qualities and of the shades indicated below may be obtained in a similar manner by condensing 2,3-dich'loro-6-quinoxa1ine-carbonyl chloride with the coupling components listed below, and then coupling to the diazotized amines tabulated.

8 Example IV.Az0 dye-Developed on the fiber A 4% solution of the green-brown coupling component, prepared from the filter cake obtained in the first step of Example III, is padded on cotton fabric at 50% pick-up. The fabric is dried, padded at 50% pick-up with a 1.5% aqueous solution of sodium carbonate, steamed for 30 seconds, and rinsed. The treated fiber is then immersed in a cold diazo solution of 2-amino-p-benzenedisulfonic acid (prepared in known manner from the amine, HCl and NaNO containing sufiicient alkali to effect coupling with the coupler applied to the fiber. The latter is then scoured, rinsed and dried. A red dyeing is obtained, identical in shade and fastness with that obtained by the dye of Example III(b).

If the diazo compound in the above coupling bath is replaced by the diazo compound of any of the following amines, dyeings of the shades indicated below and of good fastness qualities are obtained.

TABLE IV Diazo component: Shade on fiber 4 amino 2 methylbenzenesulfonic acid Blue-red. 4 amino 3 methylbenzenesulfonic acid Blue-red. 2 amino 3,6 naphthalenedisulfonic acid Maroon. 2,5 dimethoxyaniline Blue-purple. 2 methoxy 5 methylaniline Purple. 4 methoxy 2 nitroaniline Brown. 2 methoxy 4 nitroaniline Purple. 0 Anisidine Maroon.

p Anisidine Maroon. 3 amino 4 methoxybenzenesultonic acid Maroon.

p Nitroaniline Maroon. Orthanilic acid Red. 2,4 dichloroaniline Red.

Example V.Azo dyesalternate process-condensing the carbonyl halide with the component to be diazotized Preparation of the diazo solution.3.6 parts of 2,4- diamino-benzenesulfonic acid are dissolved in parts of water. 5 parts of 2,3-dich1oro-@quinoxalinecarbonyl chloride are then added at 20 to 25 C. and pH 7 to 8 over a period of 4 hours. The resulting solution is cooled to 5 C., and the pH is adjustd to 5.2 by addition of 2 N hydrochloric acid. The condensation product thus obtained is diazotized in the usual manner with hydrochloric acid and sodium nitrite, at 5 to 10 C. After stirring for 1 hour at 5 to 10 C., the excess nitrite is destroyed. The pH is then adjusted to 5.1 with an aqueous solution of sodium bicarbonate.

Preparation of coupling component and coupling step.-5.4 parts of 6-acetamido-1-naphthol-3-sulfonic acid are dissolved in 100 parts of water. The pH of the solution is adjusted to 7.2 with a solution of sodium bicarbonate, followed by the addition of 4 parts of sodium bicarbonate. The above mentioned diazo solution is stirred into the solution of coupling component, at room temperature, to give a bright orange colored solution. Upon addition of sodium chloride (sufiicient to form a 15 salt solution) an orange precipitate is obtained, which is filtered off, washed with 20 parts of 10% sodium chloride solution, and dried. The product corresponds to the formula OH SO N-a l I N N N \C C1 CHaC O-NH SO;H3 NN C O 43-431 When applied to cotton by any of the procedures A t C below, it produces bright orange dyeings which exhibit excellent fastness to light and to washing.

It the above procedure is repeated except that the 2,4- diaminobenzene-sulfonic acid is replaced by 3.6 parts of 2,5-diaminobenzene-sulfonic acid, the quinoxaline-carbonyl chloride is replaced by 5 parts of 1,4-dichloro-6- phthalazine-carbonyl chloride and the condensation of these two compounds is performed in 15 parts of water, a dye of the following formula is obtained:

When applied to cellulosic fiber by the above alluded to fiber-reactive procedures, this dye gives bright scarlet dyeings having excellent fastness to light, washing and acid perspiration tests. a

In a similar manner, dyes of the shades indicated below and of excellent fastness properties may be produced by using, in the procedure set forth hereinabove, the following diamines and coupling components.

The dyes in this example and table may also be produced directly on the fiber, for instance by first fixing onto the fiber (by any of procedures A to C below) the condensation product of any of the above diamines with a dihalogen benzodiazine halide, then diazotizing on the fiber and developing with any of the above tabulated couplers.

Example VI.--Metallized azo dye-CopperBy condensing with the intermediate 4.6 parts of J acid (6-amino-1-naphthol-3-sulfonic acid) are stirred overnight with parts of 1,4-dichloro-6-phthalazine-carbonyl chloride in 200 parts of water at pH 8, at room temperature. The condensation product is salted out, filtered 01f, washed with 5% NaCl solution and dried. The product thus prepared is dissolved in 200 parts of Water, the solution is adjusted to pH 7.5 (with sodium bicarbonate) and then cooled to 15 C. This comprises the coupling component for the azo dye.

3.6 parts of 2-amino-1-phenol-4-sulfonic acid in 100 parts of water are diazotized at 5 C. in the usual manner with HCl and sodium nitrite. After a 1 hour period, the excess nitrite isdestroyed. The pH of the solution is Metallization.--To the resulting orange solution of the monoazo dye at 25 C. arev added 3.05 parts of copper sulfate (CuSO in parts of water at pH 7. The rubine solution is stirred for 2 hours at C. and salted to 8% (8 parts NaCl per 100 parts of solution) to give a rubine solid which is filtered oif, rinsed and dried.

The dye thus obtained has the structure O-Cn o 01 I N=N \N I mots NaOi NH-C o 2 When applied to cotton fiber by fiber reactive procedure as discussed above, it gives a rubine shade of excellent wash, light and bleach fastness.

Example VII.Metallized azo dyeC0pper-By condensing with the metallized dye Diazotization and c0upling.-3.6 parts of 2-amino-lphenol-4-sulfonic acid in 100 parts of water are diazotized adjusted to 7.5 with sodium bicarbonate and the temperas in 'Example VI and coupled, at pH 9 to 10, to 4.6 parts of J acid in 200 parts of water. The pH is then adjusted to 6.5, and 2 parts of sodium acetate are added.

Metallizati0n.To the buifered solution thus obtained are added 3.05 parts of copper sulfate; the temperature is raised to C. and is held for '1 hour. The resulting rubine solution is salted to 15% using NaCl, and the rubine solid is filtered off and washed with 50 parts of saturated salt solution.

Condensation.The rubine solid from above is dissolved in 300 parts of water at 15 to 20 C. The pH is adjusted with sodium bicarbonate to pH 7 to 8, and is maintained at this value while the mass is condensed with 5.0 parts of 1,4-dichloro-6-phthalazine-carbonyl chloride.

After stirring overnight at room temperature, the condensation is complete. The solution is salted to 8% NaCl concentration, and the rubine dye is filtered oif, washed and dried as above. Its structure is the same as in part A of this example.

Example VIIl.-Met allized azo dyeChr0mium Diazotization and c0upling.--5.46 parts of l-amino-6- nitro2-naphthol-3-sulfonic acid are diazotized in 200 parts of water at 5 to 10 C. with HCl and NaNO The temperature is allowed to warm slowly to 15 to 20 C., the excess nitrite is removed by aid of sulfamic acid, and the pH is adjusted to 7 with solid sodium formate. This is the diazo solution.

4.6 parts of J acid are dissolved in parts of water, and the pH is adjusted to 9.3 by the addition '10 N Na CO solution. This is thecoupler solution. I

The above diazo solution is added to the solutiono coupler over a 1 hour period while maintaining the pH at 9 to 10. The coupling reaction is completed by continued stirring overnight at this pH.

Metallization.--The pH of the above solution of amino azo dye is now adjusted to 7.0 with 10 N HCl. 2.0 parts of sodium acetate and 20 parts of a solution of sodium chromosalicylate containing 2.5% chromium are added. The solution is refluxed for 4 hours and results in a greenish gray solution.

Condensation.The greenish gray solution is adjusted dichloro-6-quinoxaline-carbonyl chloride, at 40 to 50 C.,

overnight. The mass is now salted to 10% NaCl concentration; the gray solid is filtered off, washed with 25 parts of 10% NaCl solution and dried.

11 The gray solid, thus obtained corresponds to the formula NaOsS When dyed on cotton by the various application methods discussed above, it yields a greenish gray shade which has good light, wash and bleach fastness.

Example IX .Acid antlzraquinone dye 28 parts of l-amino-4-(3-amino-4-sulfoanilino)-2-anthraquinone-sulfonic acid (prepared by the condensation of 1-amino-4-bromo-2-anthraquinone-sulfonic acid with 2,4 liaminobenzene-sulfonic acid) are dissolved in 3000 parts of water, and the pH of the solution is adjusted to 7.2 by the addition of a concentrated solution of trisodium phosphate. 15 parts of 2,3-dichloro-6-quinoxaline-carbonyl chloride are added to the blue solution, over a 35-hour period, at 35 to 45 C., while maintaining the pH at 7 .5 to 8.5 by the addition of trisodium phosphate. The resulting thick slurry is allowed to cool to room temperaturewhile stirring overnight. After salting with 300 parts of sodium chloride, the blue precipitate is filtered oiT, washed with 50 parts of a 4% sodium chloride solution, and dried in a vacuum desiccator below 60 C. The product is a sodium salt of the compound defined by the formula When applied to cotton fiber by the procedures of Examples A to C below, it produces bright blue dyeings of excellent fastness to light, washing and acid perspiration.

A dye of substantially the same shade and qualities is obtained if the quinoxaline compound in the above example is replaced by 15 parts of 1,4-dichlor-6-phthalazine-carbonyl chloride.

Example X 29.8 parts of l-amino-4-(4-methylamino-3-sulfoanilino)-2-anthraquinonesulfonic acid (prepared by the condensation of 1-amino-4-bromo 2 anthraquinonesulfonic acid with 4-methylamino-3-sulfoaniline) are condensed as in Example IX with 15 parts of 2,3-dichloro-6-quinoxaline-carbonyl chloride. The product is recovered as in Example IX and constitutes a sodium salt of a compound defined by the formula 0 NH, II I SO;H

I I (3H3 0-01 When applied to cotton by the procedures of Part III hereinbelow, this compound produces bright blue dyeing of excellent fastness to light, washing and acid perspiration.

Dyes of similar fastness qualities and of shades as indicated below are obtained if the procedure of Example 12 IX is repeated with any of the following acid anthraquinone dyes as initial materials:

Example XI.-Phthal0cyanine dye Preparation of water-soluble copper phthalocyanine intermediate.5.76 parts of copper phthalocyanine are slowly added below 25 C. to 41 parts of chlorosulfonic acid. The solution is slowly heated to 130 C., and held for 3 hours, cooled, and drowned below 5 C. in an agitated mixture consisting of parts of cold water, 300 parts of ice and 35 parts of sodium chloride. The solid is then filtered off and washed with 500 parts of 5% sodium chloride solution. This represents copper phthalocyanine polysulfonyl chloride press cake,

This press cake is now slowly added at pH 6 to 6.5 (maintained by the addition of sodium carbonate) to a solution of 4.34 parts of p-phenylenediamine in 40 parts of water. The turquoise solution is warmed and agitated at. 60 C., until the pH remains constant. The reaction mass is then cooled and salted to 20% salt concentration by addition of soduim chloride. The solid is filtered off and washed with 100 parts of 15% salt solution. It constitutes a compound of the formula s OzNH-O-Nllz) CuPc (SO3NB)! wherein x and y are average numbers of which x is not less than 1, y is not less than 2, and the sum of the two is between 3 and 4, while CuPc represents a molecule of copper phthalocyanine less (x-l-y) H-atoms.

C0ndensati0n.The filter cake obtained above is dissolved 'in 200 parts of water, the pH is adjusted to about 7.5 to 8 by addition of sodium bicarbonate, the temperature is raised to about 40 to 50 C. and 5.2 parts of 2,3- dichloro-6-quinoxalinc-carbonyl chloride are added. The condensation is allowed to proceed for 12 to 15 hours under agitation at said temperature. The solution is salted to 15% sodium chloride. The resulting turquoise dye is filtered off, washed with 50 parts of 20% salt solution and dried.

The dried cake represents a compound of the formula hereinabove, but wherein at least some of the -SOzNH-ONH2 groups have been replaced by side-chains of the formula When applied to cotton by the methods outlined above, it afiords bright turquoise shades that are fast to washing and to light.

Similar results as in the above example may be obtained by starting with a sulfuric acid-stable metal phthalocyanine, such as nickel or cobalt phthalocyanine, in lieu of copper phthalocyanine. Also, by changing the nature of the diamine selected, the quantity thereof, and

'13 the-conditions of chlorosulfonation, phthalocyanine compounds of the general formula may be obtained and used as initial dye for condensation with dihalogeno-benzodiazine-carbonyl halides. In this formula, x and y are average numbers adding up to between 2 and 4 (each being at least 1); MPc represents a metal phthalocyanine which is stable in the chlorosulfonation reaction (for instance, nickel or cobalt phthalocyanine), while Ar may represent miscellaneous substituted phenylene diamines, 'benzidines or diaminostilbenes, as typified by the following table.

TABLE VII 7 2,5-diaminobenzene-sulfonic acid; N-methyl-p-phenylenediamine; Y N-2-hydroxyethyl-p-phenylenediamine; N-2-cyanoethyl-p-phenylenediamine; N-2-sulfatoethyl-p-pheny1enediamine; S-amino-2-ethylaminobenzene-sulfonic acid; 4,4'-diamino-3-3'-biphenyl-disulfonic acid;- 5-amino-2-n-propylamino-benzenesulfonic acid; 4,4'-d iamino-2,2'-biphenyl-disulfonic acid; 4,4-diamino-2,2'-stilbene-disulfonic acid; m-Phenylenediamine; 2,4-diaminobenzenesulfonic acid; N-methyl-mphenylenediamine;

N- (2-hydroxyethyl -m-pheny1enediamine; N-isobutyl-mrphenylenediamine; 4-amino-2-methylamino-benzenesulfonic acid; 4-amino-2-n-butylamino-benzenesulfonic acid; Toluene-2,5-diamine; I Toluene--2,4-diamine.

Similar results are obtained further by using in lieu of the sulfamido-arylamino-su'bstituted phthalocyanines above formulated, phthalocyanine compounds which bear amino groups on an aliphatic side-chain, for instance the compound (CHiNHTHCl)? GuPc (503E): (U.S.P. 2,761,868)

Example XII Copper phthalocyanine polysulfonyl chloride press cake, obtained as in Example XI from 5.76 parts of copper phthalocyanine, is slurried at pH 6 and 40 C. in 150 parts of water containing 4.1 parts of the condensation product of 2,4-diamino-benzenesulfonic acid with 2,3 dichloro 6 quinoxaline carbonyl chloride (prepared as in Example V). After four hours stirring at this temperature and pH, the blue solution is salted, and thedye is filtered off and dried. It constitutes a sodium salt of the dye represented in the free acid form by the formula wherein x and y are average numbers of which at is not methods of part III hereinbelow, this dye produces bright turquoise shades, which are fast to washing and to light. In lieu of 2,4-diamino-benzenesu1fonic acid in the above condensation, other arylene diamines may be used, for instance, p-phenylene diamine, m-phenylene diarmne, or 2,5-diaminobenzene-sulfonic acid.

PART IH.'APPLICATION TO FIBER One-pad pr0cedure.-Cotton fabric is padded with a solution of the dye, urea and sodium carbonate and/or sodium bicarbonate. The padding is cured by steaming for 15 seconds or more, thereafter cooled, rinsed, scoured, rinsed and dried.

Specific examples illustrating this process are as folv lows: 1

' Example A ExampleB Two parts of 'the'dye of Example X are dissolved in 1000'parts of water containing 10 parts of sodium bicarbonate and 50 parts of urea. .This solution is padded onto cotton corduroy at pick-up, the fabric is immediately passed through a 220 F. steamer for 30 seconds, washed and dried. There results a light blue dyeing which is fast to washing and light.

When the urea is omitted from the dye bath, a dyeing of equal shade, strength and fastness results.

Example C Ten parts'of the dye of Example -IH paragraph C, are dissolved in 1000 parts of water containing 20 parts of sodium carbonate. This solution is padded onto cot-.

ton terry cloth, the fabric is squeezed, immediately steamed for 45 seconds at 212 F., washed and dried. There results a bright red dyeing which is fast to washing and light.

ExampleD 60 parts of the dye of Example XII are dissolved in 1000 parts ofwater containing five parts of sodium carbonate and 15 parts of sodium bicarbonate. This solution is padded onto cotton .terry cloth at pick-up. The fabric is steamed for 30 seconds at 230 F., washed and dried. There results a bright turquoise dyeing which is fast to washing.

It is to be understood that any of the dyes in the above Examples I to XII or prepared from the intermediates in Tables I to VII can be used in any of the procedures shown in Examples A to D to give essentially the same results.

It will be understood that the details of the above examples may be varied widely without departing from the spirit of this invention.

The azo dyes named in Examples I and II, may be replaced by theoretically equivalent quantity of any azo dye having the requisite water-solubility byvirtue of possessing sulfo and/or carboxy groups and having an acylatable amino group. Likewise, the diazo components and coupling components named in Examples III and IV may be replaced by theoretically equivalent quantities of any combination of a diazo component and a coupling component which will result in a dye having the requisite water-solubility. Some alternatives have been specifically named in the mentioned examples.

Others worthy 'of special consideration, because they are readily available or lead to desirable shades, are indicated in the following tables of diazo components and coupling components and by the azo dyes which result from coupling these in various combinations from these Alternative diazo-azo components:

4-amino-4'-nitro-2,2-stilbenedisulfonic acid l-naphthol-3,6,8-trisulfonic acid (and reduction of the 4'- nitro group to an amino group);

2-amino+p-benzenedisulfonic acid- 5amino-2-naphthalenesulfonic acid;

Sulfanilic acid' orthanilic acid;

2-amino-4-nitrobenzene-sulfonic acid cresidine;

3-amino-1,S-naphthalene-disulfonic acid cresidine.

In Example V, any of the diam-nines there named may be replaced by mphenylene-diarnine or p-phenylene-diamine, while the coupling components may be replaced by any of the alternatives named hereinabove as well as by 6- or S-acetamido-1-naphthol-3-sulfonic acid, S-acetarnido-1-naphthol-3,6-disulfonic acid, 8-benzamido-1-naphthol-3 ,6-disulfonic acid, 7-amino-1-naphthol-3,6-disulfonic acid, 6-amino-1,3-naphthalenedisulfonic acid, 2-naphthol-3,6-disulfonic acid, or 3=amino-2,7-naphtha1enedisulfonic acid.

In Examples VI, VII and VIII, the metallizing agents (Cu and Cr) may be interchanged or they may be replaced by reagents which will introduce nickel or cobalt as metal into the azo dye. The latter itself (in each example) may be replaced by other metallizable azo dyes, for instance, any of the following:

2-amino-1-phenol-4-sulfonic acid, diazotized and coupled 7-amino-l-naphthol-S-sulfonic acid, or to S-methylamino-1-naphthol-3-sulfonic acid, or to S-amino- 1-naphthol-3,6-disulfonic acid;

2-amino 1 phenol-4,6-disulfonic acid-a 6-amino-1- naphthol-3sulfonic acid;

2 amino-l-phenol-S-sulfonic acid-+6-(3-amino-4-s'ulfoanilino)-1-naphthol-3 sulfonic acid;

2-amino-4-methyl-1-phenyl-5-sulfonic acid- 6-arninol-naphthol-3-sulfonic acid;

2-amino-4-sulfobenzoic acid- G-amino l naphthol- 3-sulfonic acid;

Z-amino-6-nitro-phenol-4-sulfonic acid- 6-(4-amino- 3-su1foanilino)-1-naphthol-3-sulfonic acid;

2 amino-6-nitro-l-phenol-4-sulfonic acid- 3-methyl- 1-(p-sulfophenyl)-5-pyrazolone (and reduction of the nitro group to an amino group);

2 amino-S-rritrobenzoic acid- 3-methyl-l-(p-sulfopheny1)-5-pyraz01one (and reduction of the nitro group to an amino group);

,l-amino 6 nitro-2-naphthol-4-sulfonic acid- 8- amino-l-naphthol-jqsulfonic acid;

16 l amino-6-nitro-2-napththol-4-sulfonic acid, diazotized and coupled to: 2-naphthol-6-sulfonic acid or 3-methyll-(m-sulfophenyl)-5-pyrazolone, and followed in each instance by reduction of the nitro group to an amino group.

In Examples IX and X, the acid anthraquinone dyes named there may be replaced by any other dyes of this class, for instance any one of the following:

1-arnino-4-( 3 -methylamino-4-sulfoanilino -2- anthraquinonesulfonic acid; 1-amino-4- 3-amino-2-n1ethyl-5-sulfoanilino -2- anthraquinonesulfonic acid; 1-amino-4-(m-aminoanilino)-2,6- or 2,8-anthraquinone-disulfonic acid; 1-amino-4-(p-aminoanilino)-2,3-, 2,6- or 2,8-anthraquinone-disulfonic acid; 1-amino-4-(3-amino-4-sulfoanilino)-2,6- or 2,8-

anthraquinone-disulfonic acid; 1-amino-4-(4-amino-3-sulfoanilino)-2,6-anthraquinone-disulfonic acid; 1-amino-4-(p,n-butylamino-anilino)-2,6-anthraquinone-disulfonic acid; 1-amino-4-(p-beta-hydroxyethylamino-anilino)-2,5-

anthraquinone-disulfonic acid; 1-amino-4-(p-beta-cyanoethylamino-anilin0)-2,3- anthraquinone-disulfonic acid; 1-arnino-4- (p-beta-sulfatoethylarnino-anilino -'2,3-

anthraquinone-disulfonic acid; 1-amino-4-(3-carboxy-4-rnethylaminoanilino)-2,6-

anthraquinone-disulfonic acid; 1,4-bis(4-amino-3-sulfoanilino)-anthraquinone; 1-amino-4- Z-carboxyanilino -3 -anthraquinonesulfonic acid; 1-amino-4-[p-(4-amino-3-sulfophenyl)anilino]-2,5

anthraquinone-disulfonic acid; 1-amino-4-[4-(4-amino-2-sulfopheny1)-3-sulfoanilino]- 2-anthraquinonesulfonic acid; 1-amino-4- 4-amino-2-sulfostyryl -3 -sulfoanilino] 2-anthraquinonesulfonic acid; 4,8-bis(4-amino-3-sulfoanilino)-1,5-dihydroXy-2,6-

anthraquinone-disulfonic acid; 1-amino-4- [p-( 4-amino-2-sulfophenylazo) anilino] 2,5-anthraquinone-disulfonic acid;

The acid-anthraquinone dye of formula (I? ITIH:

In the salting out step in each example, the quantity of salt employed may vary Widely, and this can be readily determined by observing the volume or rate of precipitation of the dye. In some instances, where the solid dye product separates readily on cooling, the salting step may be omitted altogether.

The salted out dye in any of the examples may be con! verted into free SO H form by acidification and the latter may then be converted into water-soluble salts by treatment with customary, Water-soluble bases, for instance, NaOH, KOH, ammonium hydroxide or water-soluble organic amines.

17 In selecting the dye chromophore, it may be well to observe that those compounds wherein the R in the group is an alkyl radical of 1 to 4 C-atoms and wherein the remainder of the dye molecule is free of OH, NH and NH groups, generally lead to fiber reactive dyes which possess'high fastness to bleach, in addition to good lightand wash-fastness. (See Example H and Table 11 above.)

In lieu of the acid acceptors for the condensation reaction named in the specific examples (i.e. sodium bicarbonate or trisodium phosphate), other bases may be employed, such as sodium hydroxide, potassium carbonate, sodium acetate, ammonium hydroxide and the like. The pH for this reaction is not particularly critical, the operable range being approximately between pH 4 and 10, and the preferred range being about pH 7 to 9.

In the application of the dye to the fiber, the alkalizing treatment may he achieved by commonly used acid acceptor, for instance, sodium or potassium carbonate and similar alkali-metal bicarbonates;

Other permissible variations will be readily obvious to those skilled in the art.

The majority of the reactive dyes of this invention are characterized by high percentage fixation and high rate of fixation on cellulosic fiber; they also possess alkaline stability, which implies little if any loss by decomposition in the pad bath treatment.

By acid anthraqninone coloring matters we mean any water-soluble anthraquinone coloring compound, particularly those which are normally used as acid wool c01- ors. See, for instance, H. A. Lubs, The Chemistry of Synthetic Dyes and Pigments, chapter on Anthraquinone Acid Dyes, pages 390 to 417, inclusive.

'By water-soluble phthalocyanine coloring matters, we mean compounds having the fundamental macrocyclic structure of a metal phthalocyanine, for instance, that of Cu[C H (CN) bearing sufiicient water-solubilizing groups to solubilize the compound to the extent needed in a dyebath, as above indicated.

By anionic dye chromophore we mean a dye which bears anionic water-solubilizing radicals such as sulfo or carboxy.

The preceding representative examples may be varied within the scope of the present total specification disclo- 5 sure, as understood and practiced by one skilled in the art, to achieve essentially the same results.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this 10 invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

'1. A single pad-steam process for dyeing cellulosic materials with a fiber-reactive dye containing a 2,3-dichloro-6-quinoxalinecarbonylamino group which process consists essentially of the following steps:

(A) the cellulosic material is padded with said fiberreactive dye from a solution consisting essentially of from 0.1 to 60 parts of said dye and from 10 to 20 parts of an acid acceptor selected from the group consisting'of sodium carbonate and sodium bicarbonate, per 1000 parts of water, at ambient temperature;

(B) the resulting dye-padded material is then steamed for at least seconds at a temperature of from 212 to 240 F.; and

(C) the dyed fabric of Step B is then washed.

2. The process of claim 1 conducted in the presence 30 of urea.

References Cited by the Examiner UNITED STATES PATENTS NORMAN G. TORCHIN, Primary Examiner.

T. J. HERBERT, Assistant Examiner. 

1. A SINGLE PAD-STEAM PROCESS FOR DYEING CELLULOSIC MATERIALS WITH A FIBER-REACTIVE DYE CONTAINING A 2,3-DICHLORO-6-QUINOXALINECARBONYLAMINO GROUP WHICH PROCESS CONSISTS ESSENTIALLY OF THE FOLLOWING STEPS: (A) THE CELLULOSE MATERIAL IS PADDED WITH SAID FIBERREACTIVE DYE FROM A SOLUTION CONSISTING ESSENTIALLY OF FROM 0.1 TO 60 PARTS OF SAID DYE AND FROM 10 TO 20 PARTS OF AN ACID ACCEPTOR SELECTED FROM THE GROUP CONSISTING OF SODIUM CARBONATE AND SODIUM BICARBONATE, PER 1000 PARTS OF WATER, AT AMBIENT TEMPERATURE; (B) THE RESULTING DYE-PADDED MATERIAL IS THEN STEAMED FOR AT LEAST 15 SECONDS AT A TEMPERATURE OF FROM 212 TO 240*F.; AND (C) THE DYED FABRIC OF STEP B IS THEN WASHED. 